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Eddy-covariance measurements of carbon dioxide fluxes were taken continuously between October 2006 and May 2008 at 190 m height in central London (UK) to quantify emissions and study their controls. Inner London, with a population of 8.2 million (~5000 inhabitants per km<sup>2</sup>) is heavily built up with 8% vegetation cover within the central boroughs. CO<sub>2</sub> emissions were found to be mainly controlled by fossil fuel combustion (e.g. traffic, commercial and domestic heating). The measurement period allowed investigation of both diurnal patterns and seasonal trends. Diurnal averages of CO<sub>2</sub> fluxes were found to be correlated with traffic but also exhibited an inverse dependency on atmospheric stability in the near-neutral range, with higher fluxes coinciding with unstable stratification during most seasons and perhaps reflecting how changes in heating-related natural gas consumption and, to a lesser extent, photosynthetic activity controlled the seasonal variability. Despite measurements being taken at ca. 22 times the mean building height, coupling with street level was adequate, especially during daytime. Night-time saw a higher occurrence of stable or neutral stratification, especially in autumn and winter, which resulted in data loss in post-processing and caused the tower to become decoupled from street level. CO<sub>2</sub> fluxes observed at night were not always correlated with traffic counts, probably reflecting this decoupling, but also the fact that at night heating was always a larger source than traffic. No significant difference was found between the annual estimate of net exchange of CO<sub>2</sub> for the expected measurement footprint and the values derived from the National Atmospheric Emissions Inventory (NAEI), with daytime fluxes differing by only 3%. This agreement with NAEI data also supported the use of the simple flux footprint model which was applied to the London site; this also suggests that individual roughness elements did not significantly affect the measurements due to the large ratio of measurement height to mean building height.
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Using a new reconstruction of the solar proton energy spectra for Ground Level Enhancement (GLE) events, based on fits to measurements from ground-based and satellite-borne instruments covering a wide energy range, we quantitatively evaluate the possible ionization effects in the low and middle atmosphere for 58 out of the 66 GLE events recorded by the world-wide neutron monitor network since 1956. The ionization computations are based on the numerical 3D CRAC:CRII model. A table of the ionization effect caused by the GLE events at different atmospheric heights is provided. It is shown that the direct ionization effect is negligible or even negative, due to the accompanying Forbush decreases, in all low- and mid-latitude regions. The ionization effect is important only in the polar atmosphere, where it can be dramatic in the middle and upper atmosphere (above 30 km) during major GLE events.
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The 2008 Antarctic ozone hole was one of the largest and most long-lived in recent years. Predictions of the ozone hole were made in near-real time (NRT) and hindcast mode with the Integrated Forecast System (IFS) of the European Centre for Medium-Range Weather Forecasts (ECMWF). The forecasts were carried out both with and without assimilation of satellite observations from multiple instruments to provide more realistic initial conditions. Three different chemistry schemes were applied for the description of stratospheric ozone chemistry: (i) a linearization of the ozone chemistry, (ii) the stratospheric chemical mechanism of the Model of Ozone and Related Chemical Tracers, version 3, (MOZART-3) and (iii) the relaxation to climatology as implemented in the Transport Model, version 5, (TM5). The IFS uses the latter two schemes by means of a two-way coupled system. Without assimilation, the forecasts showed model-specific shortcomings in predicting start time, extent and duration of the ozone hole. The assimilation of satellite observations from the Microwave Limb Sounder (MLS), the Ozone Monitoring Instrument (OMI), the Solar Backscattering Ultraviolet radiometer (SBUV-2) and the SCanning Imaging Absorption spectroMeter for Atmospheric CartograpHY (SCIAMACHY) led to a significant improvement of the forecasts when compared with total columns and vertical profiles from ozone sondes. The combined assimilation of observations from multiple instruments helped to overcome limitations of the ultraviolet (UV) sensors at low solar elevation over Antarctica. The assimilation of data from MLS was crucial to obtain a good agreement with the observed ozone profiles both in the polar stratosphere and troposphere. The ozone analyses by the three model configurations were very similar despite the different underlying chemistry schemes. Using ozone analyses as initial conditions had a very beneficial but variable effect on the predictability of the ozone hole over 15 days. The initialized forecasts with the MOZART-3 chemistry produced the best predictions of the increasing ozone hole whereas the linear scheme showed the best results during the ozonehole closure.
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The impact of primary sulfate emissions on cloud condensation nuclei (CCN) concentrations, one of the major uncertainties in global CCN predictions, depends on the fraction of sulfur mass emitted as primary sulfate particles (<i>f</i><sub>sulfate</sub>), the fraction of primary sulfate mass distributed into the nucleation mode particles (<i>f</i><sub>nucl</sub>), and the nucleation and growth processes in the ambient atmosphere. Here, we use a global size-resolved aerosol microphysics model recently developed to study how the different parameterizations of primary sulfate emission affect particle properties and CCN abundance. Different from previous studies, we use the ion-mediated nucleation scheme to simulate tropospheric particle formation. The kinetic condensation of low volatile secondary organic gas (SOG) (in addition to H<sub>2</sub>SO<sub>4</sub> gas) on nucleated particles is calculated based on our new scheme that considers the SOG volatility changes arising from the oxidation aging. Our simulations show a compensation effect of nucleation to primary sulfate emission. We find that the change of <i>f</i><sub>nucl</sub> from 5% to 15% has a more significant impact on the simulated particle number budget than that of <i>f</i><sub>sulfate</sub> within the range of 2.5–5%. Based on our model configurations, an increase of <i>f</i><sub>sulfate</sub> from 0% to 2.5% (with <i>f</i><sub>nucl</sub> = 5%) does not improve the agreement between simulated and observed annual mean number concentrations of particles >10 nm at 21 stations but further increase of either <i>f</i><sub>sulfate</sub> from 2.5% to 5% (with <i>f</i><sub>nucl</sub> = 5%) or <i>f</i><sub>nucl</sub> from 5% to 15% (with <i>f</i><sub>sulfate</sub> = 2.5%) substantially deteriorates the agreement. For <i>f</i><sub>sulfate</sub> of 2.5%–5% and <i>f</i><sub>nucl</sub> of 5%, our simulations indicate that the global CCN at supersaturation of 0.2% increases by 8–11% in the boundary layer and 3–5% in the whole troposphere (compared to the case with <i>f</i><sub>sulfate</sub>=0).
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The VAMOS Ocean-Cloud-Atmosphere-Land Study Regional Experiment (VOCALS-REx) was a major field experiment conducted in spring of 2008 off southern Peru and northern Chile, aimed at better understanding the coupled climate systems of the southeast Pacific. Because of logistical constrains, the coastal area around 30° S was not sampled during VOCALS-REx. This area not only marks the poleward edge of the subtropical stratocumulus cloud regime (thus acting as a source of transient disturbances) but is also one of the most active upwelling centers and source of surface ocean kinetic energy along the Chilean coast. To fill such an observational gap, a small, brief, but highly focused field experiment was conducted in late spring 2009 in the near-shore region around 30° S. The Chilean Upwelling Experiment (CUpEx) was endorsed by VOCALS as a regional component. <br><br> CUpEx included long-term monitoring, an intensive two-week field campaign and off-shore research flights. Our goal was to obtain an atmospheric/oceanic dataset with enough temporal and spatial coverage to be able to document (a) the mean diurnal cycles of the lower-troposphere and upper-ocean in a region of complex topography and coastline geometry, and (b) the ocean-atmosphere response to the rapid changes in coastal winds from strong, upwelling-favorable equatorward flow (southerly winds) to downwelling-favorable poleward flow (northerly winds). In this paper we describe the measurement platforms and sampling strategy, and provide an observational overview, highlighting some key mean-state and transient features.
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We present a detailed budget of formic and acetic acids, two of the most abundant trace gases in the atmosphere. Our bottom-up estimate of the global source of formic and acetic acids are ~1200 and ~1400 Gmol yr<sup>−1</sup>, dominated by photochemical oxidation of biogenic volatile organic compounds, in particular isoprene. Their sinks are dominated by wet and dry deposition. We use the GEOS-Chem chemical transport model to evaluate this budget against an extensive suite of measurements from ground, ship and satellite-based Fourier transform spectrometers, as well as from several aircraft campaigns over North America. The model captures the seasonality of formic and acetic acids well but generally underestimates their concentration, particularly in the Northern midlatitudes. We infer that the source of both carboxylic acids may be up to 50% greater than our estimate and report evidence for a long-lived missing secondary source of carboxylic acids that may be associated with the aging of organic aerosols. Vertical profiles of formic acid in the upper troposphere support a negative temperature dependence of the reaction between formic acid and the hydroxyl radical as suggested by several theoretical studies.
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A comprehensive aerosol characterization was conducted at Marseille during summer, including organic (OC) and elemental carbon (EC), major ionic species, radiocarbon (<sup>14</sup>C), water-soluble OC and HULIS (HUmic LIke Substances), elemental composition and primary and secondary organic markers. This paper is the second paper of a two-part series that uses this dataset to investigate the sources of Organic Aerosol (OA). While the first paper investigates the primary sources (El Haddad et al., 2010), this second paper focuses on the secondary fraction of the organic aerosol. <br><br> In the context of overall OC mass balance, primary OC (POC) contributes on average for only 22% and was dominated by vehicular emissions accounting on average for 17% of OC. As a result, 78% of OC mass cannot be attributed to the major primary sources and remains un-apportioned. Radiocarbon measurements suggest that more than 70% of this fraction is of non-fossil origin, assigned predominantly to biogenic secondary organic carbon (BSOC). Therefore, contributions from three traditional BSOC precursors, isoprene, α-pinene and β-caryophyllene, were considered. These were estimated using the ambient concentrations of Secondary Organic Aerosol (SOA) markers from each precursor and laboratory-derived marker mass fraction factors. <br><br> Secondary organic markers derived from isoprene photo-oxidation (ie: 2-methylglyceric acid and 2-methyltetrols) do not exhibit the same temporal trends. This variability was assigned to the influence of NO<sub>x</sub> concentration on their formation pathways and to their potential decay by further processing in the atmosphere. The influence of changes in isoprene chemistry on assessment of isoprene SOC contribution was evaluated explicitly. The results suggest a 60-fold variation between the different estimates computed using different isoprene SOC markers, implying that the available profiles do not reflect the actual isoprene SOC composition observed in Marseille. <br><br> Using the marker-based approach, the aggregate contribution from traditional BSOC was estimated at only 4.2% of total OC and was dominated by α-pinene SOC accounting on average for 3.4% of OC. As a result, these estimates underpredict the inexplicably high loadings of OC. This underestimation can be associated with (1) uncertainties underlying the marker-based approach, (2) presence of other SOC precursors and (3) further processing of fresh SOC, as indicated by organosulfates (RSO<sub>4</sub>H) and HUmic LIke Substances (HULIS) measurements.
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Marseille, the most important port of the Mediterranean Sea, represents a challenging case study for source apportionment exercises, combining an active photochemistry and multiple emission sources, including fugitive emissions from industrial sources and shipping. This paper presents a Chemical Mass Balance (CMB) approach based on organic markers and metals to apportion the primary sources of organic aerosol in Marseille, with a special focus on industrial emissions. Overall, the CMB model accounts for the major primary anthropogenic sources including motor vehicles, biomass burning and the aggregate emissions from three industrial processes (heavy fuel oil combustion/shipping, coke production and steel manufacturing) as well as some primary biogenic emissions. This source apportionment exercise is well corroborated by <sup>14</sup>C measurements. Primary OC estimated by the CMB accounts on average for 22% of total OC and is dominated by the vehicular emissions that contribute on average for 17% of OC mass concentration (vehicular PM contributes for 17% of PM<sub>2.5</sub>). Even though industrial emissions contribute only 2.3% of the total OC (7% of PM<sub>2.5</sub>), they are associated with ultrafine particles (<i>Dp</i><80 nm) and high concentrations of Polycyclic Aromatic Hydrocarbons (PAH) and heavy metals such as Pb, Ni and V. On one hand, given that industrial emissions governed key primary markers, their omission would lead to substantial uncertainties in the CMB analysis performed in areas heavily impacted by such sources, hindering accurate estimation of non-industrial primary sources and secondary sources. On the other hand, being associated with bursts of submicron particles and carcinogenic and mutagenic components such as PAH, these emissions are most likely related with acute ill-health outcomes and should be regulated despite their small contributions to OC. Another important result is the fact that 78% of OC mass cannot be attributed to the major primary sources and, thus, remains un-apportioned. We have consequently critically investigated the uncertainties underlying our CMB apportionments. While we have provided some evidence for photochemical decay of hopanes, this decay does not appear to significantly alter the CMB estimates of the total primary OC. Sampling artifacts and unaccounted primary sources also appear to marginally influence the amount of un-apportioned OC. Therefore, this significant amount of un-apportioned OC is mostly attributed to secondary organic carbon that appears to be the major component of OC during the whole period of study.
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Atmospheric liquid and solid water particles are stabilized if they are coated with either negative or positive electric charge. The surface charge causes an increase of the partial pressure of water vapour close to the surface of each particle, effectively allowing the particles to remain in their condensed phase even if the environmental relative humidity drops below unity. The theory, briefly presented in this paper, predicts a zero parameter relation between surface charge density and water vapour pressure. This relation was tested in a series of Electrodynamic Balance experiments. The measurements were performed by stabilizing charged droplets of pure water near an ice-surface. We observed a divergence in radius as the temperature approached the freezing point from below. We find that the measurements confirm the theory within the experimental uncertainty. In some cases this generally overlooked effect may have impact on cloud processes and on results produced by Electrodynamic Balance experiments.
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